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This review presents the nature, fundamental structure, different from partially hydrolyzed PVA [10]. In order to mod-
and various morphologies of native poly(vinyl alcohol) ify the properties of PVA, abundant hydroxyl groups play an
(PVA) matrix. It highlights recent advances in pure PVA important role [11]. The semicrystalline nature of PVA is due to
and its composites containing various nanofillers that hydrogen bonding between PVA chains [3]. PVA exists in dif-
have potential applications in various fields. Over half a ferent morphologies for variety of applications including phar-
century, PVA is known as an auspicious material for
diverse applications. The review focuses on the structural, maceutical, biomedical and others [12]. For instance, PVA gel
mechanical, optical, and electrical properties of PVA- beads may be used in water filtration systems [13]. The high
based nanocomposites. The study highlights a new prom- optical quality of PVA films is useful in optical sensors and
ising area of optoelectronics for possible applications of devices. Polymeric nanofiber membranes are being used in vari-
PVA nanocomposites. The challenges and opportunities in ety of applications including batteries, filter materials, biomedi-
working with various PVA nanocomposites are discussed cal scaffolds, fuel cells, and osmotic power plants [1, 12]. Due
along with some future recommendations are presented
to the hydrophilic nature of PVA, crosslinkers are used to syn-
to strengthen this area of research. POLYM. ENG. SCI.,
00:000–000, 2018. V
C 2018 Society of Plastics Engineers
thesize hydrogels for a number of applications [12]. To make
PVA fibers, various spinning techniques are being used. The
PVA matrix plays an essential role in the formation of such valu-
able membranes. PVA is being used to fabricate controlled inter-
INTRODUCTION connected micro porous three dimensional (3D) scaffolds for
Nanotechnology is a multidisciplinary field that has been various applications [14]. Commonly used conventional modifica-
blooming recently [1]. Its significance is increasing in various tion reactions include acetalization, carbamation, etherification, or
fields including biomedical, sensors, and computing [2]. Poly- esterification of hydroxyl group of PVA. The modern chemical
meric materials are being used as a replacement for conven- modification method is the click chemistry. The modified PVA
tional materials because they are light weight, and inexpensive may be used in a wide range of applications such as molecular
with excellent physicochemical properties [3]. Attempts are sensing in biological and biomedical fields, membranes of fuel
being made to fabricate various polymeric nanocomposites and cells, chemo sensors, absorption of toxic metals, and optoelec-
to understand their fundamental principles for their applications tronic devices [15]. Nanofillers expose their larger surface area
in various fields of science and engineering. The structural, opti- for interaction with polymer that is the key concept in the
cal, mechanical, and electrical properties of polymers can easily enhancement of functional properties of polymeric nanomaterials.
be tuned by incorporating small quantities of nanofillers in the The biomedical uses of PVA include embolization particles, eye
polymer matrices [4, 5]. Various types of polymers (like poly- drops, contact lenses, meniscus, artificial cartilage, and adhesion
ethylene, polyvinylidine fluoride, polypropylene, polymethyl barrier [16]. PVA behaves as an embedding mat and matrix for
methacrylate, polyaniline, polyvinyl chloride, polyamide, poly- metal/inorganic nanofiller for sensing, optoelectronic devices and
ethylene terephthalate, polystyrene, etc.) composites loaded with many other applications [15]. PVA nanocomposites may include
different types of nanofillers (like CuO, ZnO, ZnS, CuS, CdSe, nanofillers made from metals, nonmetals, metal oxides, metal sul-
Cds, GO, FeO, etc.) have been fabricated for structural, optical, fides, inorganic or combinations of these materials. Their applica-
mechanical and electrical properties enhancements [3, 6]. In this tions are discussed in detail in this review.
study, PVA polymer is selected due to its amazing properties
such as high optical transmission, water solubility, stable ther-
NATURE OF POLY(VINYL ALCOHOL)
mal, and noncorrosive nature that makes it a good matrix for
optoelectronic and a variety of other applications [7–9]. PVA is a creamy or whitish, tasteless, odorless, nontoxic,
In this review, the nature, physicochemical properties, mor- biocompatible, thermostable, granular or powdered semi crystal-
phologies, and means of modification of various nanocomposites line or linear synthetic polymer [3, 9, 17]. It possesses astonish-
of PVA have been discussed. A short overview of this review is ing optical properties, large dielectric strength, and excellent
presented here. Vinyl acetate as monomer is used for commer- charge storage ability [9]. Its mechanical, optical and electrical
cial PVA production. Various grades of PVA are available on attributes can readily be tailored by doping with nanofillers.
the market [7]. Completely hydrolyzed PVA has properties PVA is available on the market in different grades on the basis
of viscosity and degree of hydrolysis [7, 18]. PVA is most
widely used in the synthesis of poly(vinyl butyral) (PVB) and
Correspondence to: M. Aslam; e-mail: aslamfaridipk@gmail.com or Z.A.
Raza; e-mail: zarazapk@yahoo.com
vinylon fibers. PVB is a low cost flexible thermoplastic, being
DOI 10.1002/pen.24855 used as strong adhesive in multiple applications and might be
Published online in Wiley Online Library (wileyonlinelibrary.com). used in shape memory devices [19]. Vinylon is manmade heat
C 2018 Society of Plastics Engineers
V and chemical resistant fiber (also called Juche fiber) fabricated
Appearance Creamy to whitish, granular, powder Melting point 2308C for fully hydrolyzed,
1808C–1908C for partially hydrolyzed
Bulk density 641 kg s/m3 Boiling point 2288C
Density 1.19–1.31 g/cm3 Thermal stability Discoloration at 1008C,
darkens at above 1508C, decomposition
at 2008C
Specific gravity 1.3 (for partially hydrolyzed, highly Specific gravity 1.3 (for completely hydrolyzed, highly
viscous) [24] viscous) [24]
Stability to sunlight Excellent Glass transition temperature 758C–858C
Flammability Burns like paper Specific heat 1.5 J/(g K)
suggested to be useful as new materials for optical devices [30]. bulk properties. Due to hydrogen bonding in the matrix, PVA
Muhammad et al. [31] explored the optical properties of sodium has a high melting point. Interfaces play an important role in
nitrate (NaNO3) doped PVA nanocomposites. Doping contents understanding the behavior of materials like PVA. One disad-
of 12 wt% NaNO3 in PVA changed the refractive index of PVA vantage of working with materials in bulk form is the availabil-
(from 1.14) to 2.25, real part of dielectric constant from 1.30 (of ity of a small fraction of atoms at the interfacial surface.
PVA) to 5.10, band gap from 5.71 eV (of PVA) to 5.05 eV.
The analysis of imaginary part of dielectric constant also have PVA Hydrogels
proved that higher doping (9 and 12 wt%) of NaNO3 dissipated
A hydrogel may be defined as a crosslinked hydrophilic
more energy than at lower doping (0–6 wt%) [31]. Abdelaziz
polymer that swells in aqueous media [35]. Due to hydrophilic
and Ghannam [32] investigated the effect of titanium chloride
nature of PVA, it requires crosslinks to prepare hydrogels for a
(TiCl3) on optical and dielectric properties of PVA based com-
variety of applications [12]. The chemical crosslinkers that can
posites. Incorporating 25 wt% TiCl3 resulted in decrease in
be used in the preparation of PVA hydrogels include formalde-
impedance of PVA (from 17.3 MX) to 3.8 MX, increase in
hyde, acetaldehyde, glutaraldehyde and other monoaldehydes
dielectric constant of PVA (from 11.3) to 157 at 1 kHz, and
[12]. A variety of physical crosslinkers are available for the pro-
decrease in optical band gap of PVA of 5.2 to 3.5 eV [32].
duction of PVA hydrogels for different purposes [13]. When
Abdullah and Saleem [33] doped PVA with copper sulfide
chemical crosslinkers are used with acetic acid, methanol or sul-
(CuS) NPs and investigated their electrical and optical behavior.
The values of optical band gap was decreased from 6.27 (PVA) furic acid, acetal bridges are created in the suspended OH
to 4.77 eV on addition of 0.04 molar concentration of CuS NPs. groups of PVA chains [12]. By using a crosslinker, residual
On increasing frequency from 1 Hz to 1 MHz, the dielectric amounts may be found in the subsequent PVA hydrogel. Extrac-
constant and dielectric loss were decreased whereas, electrical tion procedures may be adopted to remove the residue material
conductivity increased. Temperature dependence (308C–1108C) to avoid harmful and toxic effects for PVA hydrogel applica-
behavior of dielectric loss, dielectric constant, and electrical tions. The solubility of PVA and its resistance to most organic
conductivity were also studied. The researchers suggested that solvents makes it suitable for a wide range of applications [11].
nanocomposites are useful in optoelectronic devices [33]. The
PVA composite materials could be utilized in different types of PVA Beads
sensors including mechanical, chemical, and biological ones [34]. Spherical PVA beads are prepared by using a saturated solu-
tion of boric acid as crosslinker and then by esterification of
MORPHOLOGIES OF PVA PVA with phosphate for solidification. A pH range of 4–6 is
Since the exploration of PVA matrix, it has been found in required for both bead strength and bead formation. A high pH
various morphologies for a variety of applications. Different is better for strength and stability of PVA beads [36]. In order
morphologies of PVA have been studied by various researchers. to remove nitrogenous toxic waste, Jeong et al. [37] conducted a
Some morphological assemblies are possible with the native study to evaluate the ability of water purification system made
PVA matrix like films formation other depends on their modi- from PVA gel beads using photosynthetic bacteria. The study
fied composition and on the processing of prepared polymer concluded that the immobilization of photosynthetic bacterial
composites. Some of such morphologies are summarized as system might be used in circulatory filtration system as one of
follows: its working components [37].
PVA Films
PVA possesses the ability to form a uniform film of high
optical quality that can be used for nonlinear optical devices
and optical sensors. PVA has got increasing interest in the field
FIG. 2. Diagram of fiber formation via electrospinning process. of photoluminescence [48]. Mieloszyk et al. [49] showed that
toxicity, biocompatibility, high hydrophilicity and easy process- via hydrogen bonding. Figure 4 shows the hydrogen bonding
ability. Hence, it is very important to modify PVA properties mechanism of metal oxides such as CuO, ZnO, Al2O3, or others
for various targeted applications. PVA can be modified chemi- with the PVA matrix. Figure 5 shows the hydrogen bonding
cally through the hydroxyl groups on the backbone. Commonly mechanism of GO nanosheets with the PVA matrix.
used conventional modification reactions include acetalization,
carbamation, etherification, or esterification of the hydroxyl PVA NANOCOMPOSITES
groups of PVA [62]. The modern chemical modification method
A polymer composite comprises of reinforcing filler and
may be click chemistry. The modified PVA material may be
polymer matrix. The dimension of fillers may be in micrometer
used in wide range of applications including molecular sensing,
or in nanometer. A polymer composite delivers such properties
biological and biomedical, the membrane of fuel cells, chemo
sensors, absorption of toxic metals and optoelectronic devices that are absent in both filler and matrix. The incorporation of
[15]. Figure 3 represents the chemical modifications of PVA fillers can modify the physicochemical properties of polymers.
having different degrees of hydrolysis and molecularmass. The type, size, shape, concentration, and mutual interaction
Awada and Daneault [62] prepared chemically modified PVA have a strong effect on the modified polymer composite. Fillers
containing tosyl, azide, and amin functional groups that were may be of various kinds including metal powders, volcanic min-
attached to the carbon backbone. Various analytical techniques erals, chalk, polymeric fibers, glass fibers, carbon fibers and
were employed to confirm the presence of these chemical modi- also natural fibers [65]. Fillers with nanodimensions are
fications [62]. regarded as smart dopant materials due to their extraordinary
One major problem in fabricating polymeric nanocomposites surface reactivity with polymers. Nanomaterials are normally
is uniform dispersion of nanofillers in polymer matrix. Uniform classified into 0, 1, 2, and 3 dimensions (D). The 0-D materials
dispersion plays a vital role in making multifunctional compo- are in the form of quantum dots, nanolenses, nano onions. The
sites and could be achieved by compounding techniques. Com- 1-D materials are found in the form of nanowires, nanobelts, or
pounding means mixing of different materials and these nanotubes. The 2-D materials are found in the form of nano-
materials may be either mixture of additives–polymers or poly- sheets, nanoplates, nanodisks or nanowalls, whereas 3-D materi-
mer–polymer. The resultant product may be a so-called blend or als are found in the form of nanocoils, nanocones, nanoballs,
composite [63]. Generally, three types of compounding techni- nanoflowers, or nanopillers [66, 67]. The combinations of nano-
ques are observed including melt compounding, in situ polymer- materials with polymers are known as polymer nanocomposites.
ization and solution blending [64]. Nanofillers (<5 wt%) are most widely used to enhance the
The PVA matrix contains abundant hydroxyl groups attached properties of polymers including toughness, strength, modulus,
to its carbon chain to allow other materials to be incorporated heat and scratch resistance, dimensional stability, thermal, and
electrical conductivity due to their high aspect ratio [68]. Nano-
fillers have advantage of possessing large surface area for inter-
action with surrounding matrix that is the key concept for the
enhancement of the properties of polymeric nanomaterials. In
addition, nanofillers possess a quantum confinement effect
which makes nanofiller–polymer interaction of great importance.
Over the last 50 years, PVA has been a candidate material for
diverse applications. PVA nanocomposites may include nanofil-
lers made from metals, nonmetals, metal oxides, metal sulfides,
inorganic, or combinations of these materials. Inorganic nanofil-
lers may include carbon nanofibers, carbon nanotubes, clays, sil-
icates and others. PVA is used as an embedding mat and matrix
for metal/inorganic nanofillers for sensing, designing of opto-
electronic devices and many other applications [15]. A few
FIG. 4. Hydrogen bonding of metal oxide with PVA matrix. PVA nanocomposites are discussed here.
Dopant Decreasing parameter values Increasing parameter values Application areas Refs.
Black tea Band gap Dispersion in refractive index Inorganic solar cells, optoelectronics [28]
CoCl2a Band gap – – [29]
ErCl3 Band gap Refractive index Optoelectronics [30]
NaNO3 Band gap Refractive index, dielectric constant, dielectric – [32]
loss
CuS Band gap, dielectric constant, dielectric loss Electrical conductivity Optoelectronics [33]
Ag Band gap, refractive index Signal intensity Biosensors, dispersion devices [41, 75]
Ferrite – Saturation magnetization EMI shielding [46]
DPL Storage modulus Tensile strength, Young’s modulus, thermal Automotive, housing, industrial usage [69]
stability
Grewia optivab – Tensile strength, thermal stability Food packaging, agricultural materials [70]
Micro algae ash – Mechanical properties, thermal properties Microalgae based biorefinery [71]
Copper Tensile strength Young’s modulus, elongation at break Charge storage devices [73]
Co-ZnO Band gap Thermal stability UV-shielding, nanophotonics [4]
Ni, Co, FeS Crystallinity – – [100]
SiC – Refractive index, microharnening – [9]
GO Band gap, contact angle Crystallinity, tensile strength, Young’s Bone tissue engineering, [5, 9, 49, 60, 82–87]
modulus, barrier properties, Urbach energy, supercapacitor electrode material, energy
refractive index, dielectric constant, storage devices, tissue engineering,
dielectric loss, optical conductivity, optoelectronics
luminescence, specific capacitance, surface
energy, thermally stable, bioactivity
RGO/ Crystallinity, band gap, melting temperature, crystallinity, tensile strength, young’s modulus, Soft electronics, supercapacitors, [18, 26, 27, 91]
Graphene crystallization temperature Urbach energy, refractive index, optical optoelectronics
conductivity, electrical conductivity, glass
transition temperature
ZnO Band gap, dielectric loss Tensile strength, elongation at break, dielectric Optoelectronics, EMI, and UV shielding, [50, 93, 95]
constant AC conductivity microwave absorption, UV luminescence
CuO Crystallinity, band gap, dielectric constant, Dispersion energy, optical conductivity – [97–99]
dielectric loss, glass transition temperature,
melting temperature, crystallization
temperature, AC conductivity
Note. Increasing/decreasing parameter values are estimated with respect to corresponding values of native PVA.
a
PVA-PPY.
b
Corn starch-PVA.